The present invention is directed to a highly filled TiS.sub.2 - polymer bonded electrodes useful in a non-aqueous battery and to a battery system containing said electrodes.
Storage batteries have a configuration composed of at least one pair of electrodes of opposite polarity and, generally, a series of adjacent electrodes of alternating polarity. The current flow between electrodes is maintained by an electrolyte composition capable of carrying ions across electrode pairs.
Non-aqueous batteries have certain distinct advantages over other types of storage batteries. They use, as anodes, light weight metals, such as lithium, lithium-aluminum alloys and the like which are at the far end of the electromotive series. These batteries have the potential for providing much higher gravimetric and volumetric energy densities (capacity per unit weight and volume, respectively) than other types of batteries, due to the low atomic weight of the metal and high potential for forming a battery in conjunction with suitable positive electrodes far removed from the light weight metal (alkali metal) electrode (the description herein will use batteries having lithium as the light weight metal anode although other light weight metals can be used) in the electromotive series. The battery can be formed in any conventional physical design, such cylindrical, rectangular or disc-shaped "button" cells, normally of a closed cell configuration.
The battery components of positive electrode, negative electrode and separator can be in the form of distinct alternating plates in a sandwich design or of a continuous spirally wound design as are well known. The anodic electrodes can be formed, for example, from lithium metal or its alloys on a support, such as a nickel coated screen. The electrolyte can be formed of a non-aqueous solvent of fused or solid electrolyte. Illustrative of known useful non-aqueous solvents include acetonitrile, tetrahydrofuran and its derivatives, propylene carbonate, various sulfones and mixtures of these solvents containing a light metal salt such as lithium salts as, for example, lithium perchlorate, iodide or hexafluroarsenate and the like. An additional, normally passive component of the battery is a separator membrane located between plates of opposite polarity to prevent contact between such plates while permitting electrolytic conduction. Separators are normally of the form of sheets which possess very low electronic conductivity.
Significant developments have been made in the fabrication of non-aqueous batteries. However, one of the major concerns is the lack of development of a suitable cathdoe in which the electrochemically cathodic material is present in the form of a porous, flexible, sheet material. The cathodic active material must be bonded into a unitary sheet by a material which is inert with respect to the other components of the battery as well as being inert and compatable to the active material. The bonding material must be capable of readily forming a uniform sheet in which the active material is uniformly distributed throughout the length and breadth of the sheet as well as across its thickness to provide maximum effectiveness. The bonding material must be kept to very low amounts of the total sheet material or the cathodic active material will be encompassed by the material and thereby dramatically reduce the conductivity and activity of the resultant cathodic sheet product. Even though present in only small amounts the bonding polymer must be capable of maintaining the sheet integrity and provide resistance to fractures, spalling and disintegration attributable to the expansion and contraction forces encountered in charge-discharge cycling when used in a secondary battery system.
Polymer bonded electrodes presently known have a number of deficiencies which has limited their utility and, thereby limited the acceptance of an effective non-aqueous battery system. The presently known polymer-bonded electrodes are not capable of being mass produced by a reliable, cost-effective, non-aqueous process. In addition, the majority of known polymer-bonded electrodes exhibit flaking and disintegration when the formed sheet is further processed such as when applied to a current collector and/or during assembly into a battery.
A number of bonding polymers have been considered for and used in the fabrication of cathodic polymer bonded electrodes. The most widely used material at the present time is poly(tetrafluoroethylene), commonly referred to as PTFE or by the tradename Teflon. PTFE bonded electrodes have certain drawbacks which limit their usefulness and ability to provide a highly effective product. For example, the chemical inertness of this polymer causes the fabrication of electrodes to be both difficult and laborious. Generally, it requires initially mixing the active material with an aqueous slurry of PTFE which is then doctored onto a surface and heated to high temperatures (250.degree.-400.degree. C.) to remove the water and cause bonding. The presence of water and the processing at high temperatures limits the active materials which can be used in forming the electrode product. For example, titanium disulfide, a desirable active material, is known to be unstable in the presence of water. PTFE bonded sheets tend to flake and are not free standing unless large amounts of polymer are used. The sheets are conventionally bonded to a current collector screen by pressing them together at high temperatures. This process normally produces a brittle product which tends to crack and chip. Finally, a major defect of this known class of product is its non-uniformity both in distribution of active material and of porosity. This defect is inherently due to the processing techniques required, especially the evaporation of solvent from the materials causing non-uniformity across its thickness as well as from point-to-point on the sheet product. Patents illustrating formation of polymer bonded electrodes by this technology are U.S. Pat. Nos. 3,457,113; 3,407,096; and 3,306,779.
Some work has been done to form a product from dry tetrafluoroethylene suspensions to overcome the incompatibility problems associated with water but such products require sintering at very high temperatures (e.g. 400.degree. C.) which also limits the types of active fillers which can be used. Patents illustrating this known technology are U.S. Pat. Nos. 3,184,339 and 3,536,537.
More recently polymer bonded electrodes have been formed from slurries of EPDM (ethylene-propylene-diene terpolymer) in an organic medium, such as cyclohexane (see "Elastomic Binders for Electrodes" by S.P.S. Yen et al., J. Electrochem. Soc., Vol. 130, No. 5, Pg. 1107). Other elastomeric polymers, such as sulfonated ionomers, butyl rubbers and the like have also been used in forming electrodes by a slurry technique (See U.S. Pat. No. 4,322,317). The resultant electrode products formed in this manner exhibit greater elasticity and compatability with the other battery components. However, the defects of non-uniformity of product, poor control of porosity and pore size distribution remain a problem. In addition, electrodes made by this method exhibit severe loss of activity after being subjected to only a few charge-discharge cycles as noted by the low figure of merit reported in U.S. Pat. No. 4,322,317.
It is highly desired to be able to provide a polymer bonded electrode which exhibits high charge density; which is capable of sustaining high discharge rates; and which is capable of exhibiting very low capacity loss upon charge-discharge cycling. In addition, the elctrode should be capable of being easily fabricated, exhibiting a high degree of uniformity, being flexible material which can be readily formed into desired configuration and maintaining its integrity under the conditions encountered in a battery (including expansion-contraction of cycling). Finally, it is highly desired to provide a polymer-bonded electrode which is in the form of a sheet of controlled microporosity capable of permitting entry and mobility of electrolyte therein which can thereby increase the electrode's activity.
Upon initial consideration, it might be assumed that many binding materials could be used as alternatives to the small number of materials presently used and obtain the desired results. However, although there are a large number of polymers available as binders in many applications including as electrode binders, a selection of a specific binder is not obvious to the artisan when attempting to provide a TiS.sub.2 filled cathodic electrode because of the many factors which influence the results one obtains with any particular binder. Among the major factors which influences the results obtained are: (1) the solubility of the binder in the organic electrolytes which are required in this application; (2) the chemical stability of the polymer at the electrode potential realizing that many cells are operated at different potentials; (3) the stability of the electrochemically active and electrically conductive materials used in combination with a particular binder and under the conditions needed for fabrication; (4) the ability of the polymer to bind the titanium disulfide and other particulate material into a unitary structure at very low concentrations in order to provide a cathodic electrode with good performance; (5) the ability and ease of obtaining a uniform distribution of the binder with the active material of the electrode; (6) the ability of the polymer to maintain a stable cathodic electrode capable of undergoing a multiplicity of charge-discharge cycling; (7) the number and ease of the steps required to obtain the desired cathodic electrode; and (8) the safety, availability of material and cost. Thus, selection of a polymer for use in forming a high performance electrode which contains titanium disulfide has been a difficult task because of the above factors which impose severe restrictions and limitations.
In a copending U.S. Application Ser. No. 843,347 filed Mar. 24, 1986, applicants disclosed a polymer bonded TiS.sub.2 electrode which preferably contained ultrafine conductive carbon particulate to enhance the electrical conductivity of the resultant sheet. However, the use of such high surface area conductive carbon reduces the charge density of the electrode and thus reduces the capacity of the battery system. In addition, in some instances the presence of carbon may cause electrolyte decomposition which shortens the life of the battery. The presently described sheet product provides a cathode having high electrical conductivity and electrochemical activity without the difficulties associated with the addition of conductive diluents such as carbon.
It has now been discovered that a cathodic polymer bonded electrode suitable for use in non-aqueous batteries can be readily formed in a manner which provides a superior electrode and overcomes the processing problems associated with Teflon and other presently used polymers as described above and can exhibit the highly desired features of having high charge density, being capable of sustaining high discharge rates and having very low capacity loss upon charge-discharge cycling.